Azo dyestuffs and process of making same



Patented May 26, 1925.

1 UNITED. srATrzs PATENT OFFICE.

HERMANN rmrzscrm, or BASEI), swrrznnnanqmssrenon TO SOCIETY-'15 CHEMI- cAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND:

No Drawing.

To all whom it may concern:

Be it known that I, HERMANN Fnrrzscrm, a citizen of the Swiss Confederation, and residing at Basel, Switzerland, have invented new and useful Azo Dyestuffs and Processes of Making Same, of which the following is a full, clear, and exact specification.

The present invention relates to new dyestuffs which yield valuable shades on the fibre. The, invention comprises the new dyestuffs, the method of making same, as

well as the material dyed with the new dyestufi's. f v

It has been found that new substantive polyazo-dyestu-fl's are. obtained by reacting on two molecular proportions of l-aminoaryl -pyrazolones, in any desired sequence, with 1 molecular proportion of phosgene and two molecular-proportions of diazotized azo-dyestuffs. There are thus obtained dyestuffs of the general formula:

- to the aryl nucleus and the -N:N-group to the pyrazoline nucleus, and R, and R signify radicals of azo-dyestuits which contain at least one azo-c'hromophor. They form brown-red to brown-black powders which dye unmordanted cotton yellow to red and brown tints which may be discharged with hydrosulfite-to a pure white.

AZO DYESTUFFS AND PROCESS 'MAKING SAME.

Application filed July 12, 1924. Serial- No, 725,695.

The invention is illustrated by the follow- Example 1.

Into a solution of 219 parts of 1 3-am'inophenyl-5-pyrazolone-S-carboxylic acid and 150 parts of calcined sodium carbonate in 3000parts of water phosgene is introduced at a ten'ipei'ature of about 4050 C. until a test sample can no longer be diazotized. The .urea derivative thus formed may be precipitated on adding mineral acid until the mixture just shows an acid action. It is a white powder which is sparingly soluble in water and alcohol, but easily soluble in alkalies and concentrated sulphuric acid.

232 parts of this new intermediate product are now dissolved in,3000 parts of water, while adding 170 parts of calcined sodium carbonate or 40 parts of caustic soda and 150 parts of crystallized sodium acetate. The mass is cooled with ice to about 5 C. and there is then allowed to flow in a suspension of the diazo-compound prepared from 305 parts of l-amino-3-t0luene azo-2- toluene-4-sulf0nic acid. The dyestutf thus formed is precipitated in the cold by means of common salt, filtered and dried. It is a brown-red powder which dyes cotton orangecolored tints which arevery fast to light and which are dischargeable with hydrosulfite to a pure white.

The new dyestufi' corresponds very probably with the formula.

on, on, H O o H Nl-I-CO-NH A! (E t J: H0.s-C-N=N- :-N=N--d-li N=N i=1 at doou (icon Example 2. I in a suspension of the diam-compound pro- 219 parts of 1 :3-aminophenyl-5-py razolonc- 3 -carboxylic acid are dissolved in 3000 parts of water, while adding 170 parts of calcined.

pared from 305 parts of 4-amino-3-to1uene-' azo-2'-toluene-4-sulfonic acid. The dyestufi' formed is precipitated in the cold by means of common salt, filtered, dissolved in 10000 parts of water and 200 parts of calcinedsodiuin carbonate, and finally treated at the ordinary temperature with phosgene until a test sample is no'longer diazotizable. The

dyestufi which has separated on addition. of common salt is identical with the one described in Example 1.

hEwampZc 3.

Into the solution, made alkaline with sodium carbonate, of the disazo-dyestuff which has been prepared by coupling 305 parts of diazotized 4-amino-3-toluene-az0-- 2-toluene-4-sulfonic acid with 464 parts of the urea of 1:3'-aminophenyl-5-pyrazolone- 3-carboxylic acid made as described in Example 1, there is allowed to run in the diazocompound prepared by diazotizing 691 parts of" the amlnodisazo-dyestufl which has been obtained by coupling diazotized. 2-amino- E'mampl 4.

189 'parts of 1:3'-aminophenyl-3-methyl- 5-pyrazolone are dissolved in about 3000 parts of water and 40 parts of caustic soda. Into the solution, to which previously there have been added 140 parts of crystallized sodium acetate, phosgene is introduced at a tem erature of about 40 C. until no diazotiza le amino-group is any longer present. In order that no reaction occurs which is add to congo, calcined sodium carbonate is added. The urea derivative formed is precipitated by acidification, and filtered. It is a white powder which is sparingly soluble in water, but easily soluble in alkalies and also in concentrated sulphuric acid.

A solution of 202 parts of the new compound in about 3000 parts of water and 40 parts of caustic soda is allowed to run into a neutralized sus ension of the diazo-compound prepared mm 305 parts of 4-amino- 3-toluene-azo-2'-toluene-4-sulfonic acid at a temperature of about 5 0., to which there have reviously. been added 140 parts of crysta .lized sodium acetate. After the combination is accomplished the whole'is ren dered alkaline to sodium carbonate and the dyestufi' formed is precipitated hot with common salt and filtered. It is an orangebrown powder which dyes cotton yelloworange tints which are fast to light. The dyeings drosu fite.

In an analo ous manner there are obtaineda dyestufi dyeing brown-Oran e from 1 4'-a1ninophenyl-5-pyrazolone-3-car oxylic are dischargeable by means of hyacid, phosgene, and 4-amino-azo-benzene-3'- sulfonic acid, "or a dyestufi" dyeing yellowish-red from 1:4'-aminophenyl-5-pyrazo-' 1one-3-carboxylic acid, phosgene, and 4- amino-3-n'1ethoxy phenyl-azo-2T-toluene-4'- sulfonic acid.

\Vhat I claim is 1. The process for the manufacture of substantive azo-dyestufis, consisting in reacting on two molecular proportions of l-amino-aryl-5-pyrazolones, in any desired sequence, with one molecular proportion of phos ene and two molecular proportions of diazotized azo-dyestufi's which contain at least one azo-group.

2. The process for the manufacture of substantive azo-dyestufls, consisting in re acting on two molecular vpro ortions of 1-amino-aryl-5-pyrazolone-3-c-ar oxylic acid, in any desired sequence, with one molecular proportion of phos ene and two molecular proportions of lazotized azo-dyestufl's which contain at least one azo-group.

3. The process for the manufacture of substantive azo-dyestufi's, consisting in reacting on two molecular proportions of 1 :3'-an1inophenyl-5-pyrazolone-3-carboxylic acid, in any desired sequence, with one molecular proportion of phosgene and two molecular pro 'ortions of diazotized azodyestufl's whicii contain at least one amgroup.

4. The process for the manufacture ofsubstantive az o-dyestufl's, consisting in rcacting on two molecular proportions of 1 3'-annnophenyl-5-pyrazolone-3-carboxylic acid, 1n any deslred sequence, with one 11mleculal' proportion of phosgene and two molecular proportions of diazotized monoazo-dyestufi's.

' 5. As new products the substantive polyazo-dyestufls of the general formula wherein R and R represent aryl-5-pyrazo lone radicals in which the NH-group is attached to the aryl nucleus and the N N-group to the pyrazolone nucleus, and wherein R and R signify radicals of azo-dyestuffs which contain at least one azochromophor, which dyestuffs form brow'nred to brown-black powders which dye unmordanted cotton yellow to brown and red shades which are fast to light.

6. As new products the substantive polyazo-dyestufls of the general formula wherein R and R represent aryl-5-pyrazolone-3-carboxylic acid radicals in which the -NH-group is attached to the aryl nucleus and the N:N-group to the pyraz'olone nucleus, and wherein R and R signify radicals of azo-dyestuifs which contain at least one azo-chromophor, which dyestuffs form brown-red to brown-black powders which dye unmordanted cotton yellow to brown and red shade which are fast to light. y

7. As new products the substantive polyazo-dyestuifs of the general formula I NH R -N=N' R wherein R and R represent phenyl-fi-pyrazolone-3-carboxylic acid radicals in which the NH-group is attached to the 3.-position of the phenyl nucleus and the IN=N- group to the pyrazolone nucleus, and wherein R and R .signify radicals of azo-dyestuffs which contain at least one azo-chromophor, which dyestuffs form brown-red to brown-black powders which dye unmor-.

danted cotton yellow to brown and red shades which are fast to light, and which are dischargeable with hydrosulfite to a pure white. 1

8. As new products the substantive polyazo-dyestulfs of thegeneral formula wherein R and R represent phenyl-5-pyrazolone-3-carbox'ylic acid radicals in which the -NH-group is attached to the 3-pos ition of the phenyl-nucleus and the N:N group to the pyrazolone nucleus, and wherein R and R signify radicals of mono-azodyestuffs which contain one azo-chromo'-' phor, which dyestuffs form brown-red to brown-black powders which dye unmor- YHERMANN FRITZSOHE.

Witnesses: JOSEPH SiiT'rERLIN,

MADELINE SPENGLER. 

